KR20210123536A - Method for preparing modified conjugated diene polymer - Google Patents

Abstract

The present invention relates to a method for preparing a modified conjugated diene-based polymer having excellent tensile, viscoelastic and adhesive properties with a high yield, while significantly reducing a loss of polymer product during dewatering and drying processes. The method according to the present invention includes the steps of: (S1) polymerizing conjugated diene-based monomers, or a conjugated diene-based monomer with an aromatic vinyl-based monomer, in a hydrocarbon-based solvent in the presence of a polymerization initiator to prepare an active polymer; (S2) making the active polymer react with a modifier to prepare a polymerizate containing a modified polymer; (S3) carrying out steam stripping of the polymerizate to prepare a filtered polymer product free from low-boiling point compounds; and (S4) dewatering and drying the filtered polymer, wherein a sorbitan derivative compound-containing solution is added to the filtered polymer in at least one time point selected from before the dewatering, during the dewatering and after the dewatering in step (S4).

Description

Method for preparing a modified conjugated diene-based polymer {Method for preparing modified conjugated diene polymer}

The present invention relates to a method for producing a modified conjugated diene-based polymer capable of producing a polymer having excellent tensile properties, viscoelastic properties and adhesive properties in high yield, in which polymer products lost during dehydration and drying are significantly reduced.

In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet road resistance is required as a rubber material for tires.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small tan δ and Goodrich heat generation is preferable.

As a rubber material with a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of small wet road resistance. Accordingly, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends and to increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

On the other hand, the SBR or BR is a polymerization reaction; denaturation reaction as needed; steam stripping; And it is prepared by batch or continuous polymerization including dehydration and drying, and the dehydration and drying process is generally a dehydration step using at least one dehydration device and a drying step using a drying device, as shown in FIG. 1 . There is a problem in that a significant amount of polymer is adhered to the drying apparatus in this process, and the yield is lowered.

Therefore, there is a need for a method capable of producing a modified conjugated diene-based polymer in high yield by reducing loss in the drying process without affecting the physical properties of SBR or BR, such as mechanical properties, viscoelastic properties, and compounding processability.

JP 2014-84407 A

The present invention has been devised to solve the problems of the prior art, and provides a method for producing a modified conjugated diene-based polymer capable of producing a polymer in high yield by remarkably reducing the polymer lost due to adhesion during dehydration and drying process aim to

In order to solve the above problems, the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon-based solvent in the presence of a polymerization initiator (S1); preparing a polymer including the modified polymer by reacting the active polymer with a modifier (S2); preparing a polymerization filtrate from which unreacted monomers are removed by steam stripping the polymer (S3); and a step (S4) of dehydrating and drying the polymerization filtrate, wherein the polymerization filtrate contains a sorbitan derivative compound at at least one point of time before dehydration, during dehydration, and before drying after dehydration in step (S4). It provides a method for producing a modified conjugated diene-based polymer by adding a.

In the production method according to the present invention, in performing step (S4), dehydration and dehydration and During the drying process, the phenomenon of dehydration and adhesion of the polymerization filtrate to the drying device is reduced, so that the polymer lost can be significantly reduced, and thus, the modified conjugated diene-based polymer can be prepared in high yield.

The following drawings attached to this specification illustrate preferred embodiments of the present invention, and serve to further understand the technical spirit of the present invention and the above-described invention, so that the present invention is limited only to the matters described in those drawings and interpreted it shouldn't be
1 is a flowchart schematically illustrating a conventional general dehydration and drying process in the production of a modified conjugated diene-based polymer.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Hereinafter, terms and measurement methods used in the present invention may be defined as follows unless otherwise defined.

The term “substitution” used in the present invention may mean that hydrogen of a functional group, atomic group or compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group or compound is substituted with a specific substituent, it is present in a functional group, atomic group or compound One or two or more plural substituents may be present depending on the number of hydrogens to be used. In addition, when a plurality of substituents are present, each substituent may be the same as or different from each other.

The term "before dehydration" used in the present invention refers to the time point before the start of the dehydration process after step 3, "during dehydration" refers to the time point during the dehydration process before the start and completion of the dehydration process, and "after dehydration" "Before drying" indicates a time point until the dehydration process is completed and the drying process is started. However, "before drying" herein may be a time including immediately after the start of drying in some cases.

The term “alkyl group” used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl, and butyl and isopropyl, sec-butyl) , tert-butyl and neopentyl may include all of a branched alkyl group.

The term “alkylene group” used in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

In the present invention, “cycloalkyl group” may mean a cyclic saturated hydrocarbon.

The term “aryl group” used in the present invention may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded ( It may mean including all polycyclic aromatic hydrocarbons).

The present invention provides a method for producing a modified conjugated diene-based polymer capable of producing a polymer in high yield by remarkably reducing the polymer lost due to adhesion during dehydration and drying.

The method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention comprises polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon-based solvent in the presence of a polymerization initiator to prepare an active polymer. step (S1); preparing a polymer including the modified polymer by reacting the active polymer with a modifier (S2); preparing a polymerization filtrate from which unreacted monomers are removed by steam stripping the polymer (S3); and a step (S4) of dehydrating and drying the polymerization filtrate, wherein the polymerization filtrate contains a sorbitan derivative compound at at least one point of time before dehydration, during dehydration, and before drying after dehydration in step (S4). characterized in that it is added.

Step 1 is a polymerization step of preparing a polymer including an active polymer by polymerizing a conjugated diene-based monomer. In a hydrocarbon-based solvent, a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer are polymerized in the presence of a polymerization initiator. can be done by

The conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and It may be at least one selected from the group consisting of 2-halo-1,3-butadiene (halo means a halogen atom).

The aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3- (2-pyrrolidino ethyl) styrene (3- (2-pyrrolidino ethyl) styrene), 4- (2-pyrrolidino ethyl) styrene (4- (2-pyrrolidino ethyl)styrene) and 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)styrene) may be at least one selected from the group consisting of.

The hydrocarbon solvent is not particularly limited, but may be, for example, at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.

In addition, according to an embodiment of the present invention, the polymerization initiator may be an organometallic compound, and the organometallic compound is not particularly limited, for example, methyllithium, itellithium, propyllithium, isopropyllithium, n-butyl Lithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium , cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium It may be at least one selected from the group consisting of sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

According to one embodiment of the present invention, the polymerization initiator is 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of the total monomer. Can be used. Here, the monomer may represent the content of the conjugated diene-based monomer or the total amount of the conjugated diene-based monomer and the aromatic vinyl-based monomer.

The polymerization in step (S1) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization terminal by growth polymerization reaction using anions. In addition, the polymerization in step (S1) may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes the step of polymerizing with the heat of its own reaction without optionally applying heat after adding a denaturation initiator may mean a polymerization method, and the temperature-rising polymerization may refer to a polymerization method in which the temperature is increased by arbitrarily applying heat after the addition of the modification initiator, and the isothermal polymerization is heat by adding heat after adding the modification initiator It may refer to a polymerization method in which the temperature of the polymer is maintained constant by increasing the temperature or taking heat away.

In addition, the polymerization may be carried out by selecting an appropriate polymerization method from among batch or continuous polymerization as needed.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may be carried out by further including a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, and in this case, it is applied to the reactor wall during long-term operation. It has the effect of preventing the formation of a gel. An example of the diene-based compound may be 1,2-butadiene.

The polymerization of step (S1) may be carried out in a temperature range of 80 °C or less, -20 °C to 80 °C, 0 °C to 80 °C, 0 °C to 70 °C, or 10 °C to 70 °C, for example. There is an effect of increasing the polymerization conversion rate of the polymerization reaction within.

The active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bound.

In addition, the polymerization of step (S1) may be carried out including a polar additive, and the polar additive is added in a proportion of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on 100 g of the total monomer. can do. As another example, the polar additive may be added in a proportion of 0.001 g to 10 g, 0.005 g to 5 g, 0.005 g to 4 g based on 1 mmol of the polymerization initiator in total.

The polar additive is, for example, tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether , tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethyl It may be at least one selected from the group consisting of ethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di (2-tetrahydro furyl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and in the case of including the polar additive, a conjugated diene-based In the case of copolymerizing a monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in their reaction rate.

According to an embodiment of the present invention, the step (S2) is a step of preparing a polymer including the modified polymer by reacting the active polymer prepared in the step (S1) with a modifier, wherein the reaction is using a modifier. It may be a denaturation reaction or a coupling reaction, and in this case, the denaturant may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. As another example, the modifier may be used in an amount of 0.1 mol to 10 mol, 0.1 mol to 5 mol, or 0.1 mol to 3 mol based on 1 mol of the polymerization initiator in step (S1).

In addition, in the above, 'polymer' includes a modified polymer produced by the reaction of an active polymer and a modifier, and includes additives such as hydrocarbon solvents, polymerization initiators or polar additives used in steps (S1) and (S2). It may contain a reactive monomer.

On the other hand, the modifier may be a modifier for modifying the ends of the polymer, and a specific example may be a silica affinity modifier. The silica-affinity modifier may mean a modifier containing a silica-affinity functional group in a compound used as a modifier, and the silica-affinity functional group has excellent affinity with a filler, particularly a silica-based filler, and thus a silica-based filler and It may refer to a functional group capable of interaction between functional groups derived from the denaturant.

The modifier may be, for example, an alkoxysilane-based compound, and a specific example may be an alkoxysilane-based compound containing at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. When the alkoxysilane-based compound is used as a modifier, through a substitution reaction between an anionic active site located at one end of the active polymer and the alkoxy group of the alkoxysilane-based compound, one end of the active polymer is modified to be bonded to a silyl group. Accordingly, the affinity of the modified conjugated diene-based copolymer including the first copolymer unit from the modifier-derived functional group present at one end of the first copolymer unit to the inorganic filler and the like can be improved. There is an effect that the viscoelasticity of the rubber composition containing the modified conjugated diene-based copolymer is further improved. In addition, when the alkoxysilane-based compound contains a nitrogen atom, in addition to the effect derived from the silyl group, an additional synergistic effect of physical properties derived from the nitrogen atom can be expected.

According to an embodiment of the present invention, the modifier may include a compound represented by the following formula (2).

[Formula 2]

In Formula 2, R ¹ may be a single bond or an alkylene group having 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group having 1 to 10 carbon atoms, R ⁴ is hydrogen, or an alkylene group having 1 to 10 carbon atoms. It may be a 10 alkyl group, a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R ²¹ is a single bond, an alkyl having 1 to 10 carbon atoms Rene group, or -[R ⁴² O] _j - may be, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, n is 0, 1 , or may be an integer of 2, and j may be an integer selected from 1 to 30.

As a specific example, in Formula 2, R ¹ may be a single bond or an alkylene group having 1 to 5 carbon atoms, R ² and R ³ may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁴ is It may be hydrogen, an alkyl group having 1 to 5 carbon atoms, a trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms, and R ²¹ is a single bond, or an alkyl group having 1 to 5 carbon atoms. Rene group, or -[R ⁴² O] _j - may be, R ⁴² may be an alkylene group having 1 to 5 carbon atoms, a may be an integer of 2 or 3, m may be an integer selected from 1 to 3, n may be an integer of 0, 1, or 2, in this case, m+n=3, and j may be an integer selected from 1 to 10.

In Formula 2, when R ⁴ is a heterocyclic group, the heterocyclic group may be unsubstituted or substituted with a trisubstituted alkoxy silyl group, and when the heterocyclic group is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group It may be substituted by being connected to the heterocyclic group by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxy silyl group may mean an alkoxy silyl group substituted with an alkoxy group having 1 to 10 carbon atoms.

As a more specific example, the compound represented by Formula 2 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine(N,N-bis(3-(dimethoxy(methyl)) silyl)propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(diethoxy(methyl)) silyl)propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine(N,N-bis(3-(trimethoxysilyl)propyl)-methyl -1-amine), N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine), N,N-diethyl-3-(tri Ethoxysilyl)propan-1-amine (N,N-diethyl-3-(triethoxysilyl)propan-1-amine), tri(trimethoxysilyl)amine, tri(3-(tri Methoxysilyl)propyl)amine (tri-(3-(trimethoxysilyl)propyl)amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilaneamine ( N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine), N,N-bis(3-(1H-imidazol-1-yl)propyl)-(tri Ethoxysilyl)methan-1-amine (N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine), N-(3-(1H-1, 2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine (N-(3-(1H- 1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysi lyl)propyl)propan-1-amine), 3-(trimethoxysilyl)-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl) propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1) -(3-(trimehtoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine), N,N-bis(2-(2-methoxyethoxy)ethyl )-3-(triethoxysilyl)propan-1-amine (N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propna-1-amine), N,N-bis( 3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2,5,8, 11,14-pentaoxahexadecan-16-amine), N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine (N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine), N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6, 9,12-tetraoxahexadecan-1-amine(N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1- amine), and may be one selected from the group consisting of tris(3-(trimethoxysilyl)propyl)amine.

As another example, the modifier may include a compound represented by the following formula (3).

[Formula 3]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.In Formula 3, R ⁵ , R ⁶ and R ⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 10 carbon atoms. may be, R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2 or 3, b + c ≥ 1, and A is

or

may be, and in this case, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

As a specific example, the compound represented by Formula 3 is N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl propan-1-amine)(N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine)) and 3- (4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine (3-(4,5-dihydro-1H) -imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by the following formula (4).

[Formula 4]

In Formula 4, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms including or not including an oxygen atom, and R ¹⁷ to R ²⁰ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. may be a hydrocarbon group, and L ¹ to L ⁴ are each independently a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, a ring formed may include 1 to 3 at least one hetero atom selected from the group consisting of N, O and S.

As a specific example, in Formula 4, A ¹ and A ² may each independently be an alkylene group ^{having 1 to 10, R 17} to R ²⁰ may each independently be an alkyl group having 1 to 10 carbon atoms, and L ¹ to L ⁴ is each independently a trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ are connected to each other and have 1 to 3 carbon atoms A ring may be formed, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring may contain one or more heteroatoms selected from the group consisting of N, O and S. to three may be included.

As a more specific example, the compound represented by Formula 4 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)), 3,3'-(1,1,3,3 -Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis (N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)), 3,3'-(1,1,3 ,3-Tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) )bis(N,N-diethylpropan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane- 1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-1-amine)), 3,3'-(1,1 ,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3′-(1,1,3,3-tetraethoxydisiloxane-1, 3-diyl)bis(N,N-diethylpropan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N- Diethylpropan-1-amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)), 3,3'- (1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpro Pan-1-amine) (3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)), 3,3'-(1 ,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane- 1,3-diyl)bis(N,N-dipropylpropan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N -diethylmethan-1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)), 3,3' -(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)(3,3'-(1,1,3,3) -tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis (N,N-diethylmethan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3) ,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) Bis(N,N-dipropylmethan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)) , 3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine)(3,3′-(1,1) ,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-ami ne)), 3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3′- (1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane -1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan) -1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine) (3, 3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)), N,N'-((1,1,3,3-tetra Methoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)(N,N'-((1, 1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N,N'-( (1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine )(N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl) )silanamine)), N,N'-((1,1,3,3-tetraprotooxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1 -trimethyl-N-(trimethylsilyl)silanamine)(N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1 ,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N,N'-( (1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine) (N, N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)), N, N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilane amine)(N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine )), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl -N-phenylsilaneamine)(N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1- trimethyl-N-phenylsilanamine), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane (1,3-bis(3- (1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3, 3-tetraethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane), and 1,3-bis(3-(1H) -imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3 , 3-tetrapropoxydisiloxane) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, R ²² and R ²³ are each independently an alkylene group having 1 to 20 carbon atoms, or -R ²⁸ [OR ²⁹ ] _f -, and R ²⁴ to R ²⁷ are each independently an alkyl group having 1 to 20 carbon atoms, or It may be an aryl group having 6 to 20 carbon atoms, R ²⁸ and R ²⁹ may each independently be an alkylene group having 1 to 20 carbon atoms, and R ⁴⁷ and R ⁴⁸ may each independently be a divalent hydrocarbon group having 1 to 6 carbon atoms. , d and e are each independently 0, or an integer selected from 1 to 3, d+e may be an integer of 1 or more, and f may be an integer of 1 to 30.

Specifically, in Formula 5, R ²² and R ²³ may each independently be an alkylene group having 1 to 10 carbon atoms, or -R ²⁸ [OR ²⁹ ] _f -, and R ²⁴ to R ²⁷ are each independently a carbon number 1 to 10 may be an alkyl group, R ²⁸ and R ²⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, d and e are each independently 0, or an integer selected from 1 to 3, d + e is It may be an integer of 1 or more, and f may be an integer selected from 1 to 30.

More specifically, the compound represented by Formula 5 may be a compound represented by Formula 5a, Formula 5b, or Formula 5c.

[Formula 5a]

[Formula 5b]

[Formula 5c]

In Formulas 5a, 5b, and 5c, R ²² to R ²⁷ , d and e are the same as described above.

As a more specific example, the compound represented by Formula 5 is 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine (1,4-bis(3-(3-(triethoxysilyl) ) propoxy) propyl) piperazine, 1,4-bis (3- (triethoxysilyl) propyl) piperazine (1,4-bis (3- (triethoxysilyl) propyl) piperazine), 1,4-bis (3- (trimethoxysilyl) propyl) piperazine (1,4-bis (3- (trimethoxysilyl) propyl) piperazine), 1,4-bis (3- (dimethoxymethylsilyl) propyl) piperazine (1,4- bis(3-(dimethoxymethylsilyl)propyl)piperazine), 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine(1-(3-(ethoxydimethlylsilyl) propyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine(1-(3- (ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine), 1-(3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine (1- (3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1,3-bis(3-(triethoxysilyl)propyl)imidazolidine(1,3-bis(3) -(triethoxysilyl)propyl)imidazolidine), 1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine(1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine), 1,3- Bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine(1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine), 1,3-bis(3-(triethoxysilyl)propyl)hexa Hydropyrimidine (1,3-bis(3-(triethoxysilyl)prop yl)hexahydropyrimidine) and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine(1,3-bis(3-(tributoxysilyl)propyl)-1 , 2,3,4-tetrahydropyrimidine) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by the following formula (6).

[Formula 6]

In Formula 6, R ³⁰ may be a monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³¹ to R ³³ may be each independently an alkylene group having 1 to 10 carbon atoms, and R ³⁴ to R ³⁷ are each independently a carbon number It may be an alkyl group of 1 to 10, g and h are each independently 0, or an integer selected from 1 to 3, g+h may be an integer of 1 or more.

As another example, the modifier may include a compound represented by the following formula (7).

[Formula 7]

In Formula 7, A ³ and A ⁴ may each independently be an alkylene group of 1 to 10, R ³⁸ to R ⁴¹ may each independently be an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, , i may be an integer selected from 1 to 30.

In another example, the denaturant is 3,4-bis(2-methoxyethoxy)-N-(4-(triethoxysilyl)butyl)aniline (3,4-bis(2-methoxyethoxy)-N-( 4-(trimethylsilyl)butyl)aniline), N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine (N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine), 2,4-bis(2-methoxy oxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine (2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine) and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane (3,14-dimtehosy- 3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane) may include one or more selected from the group consisting of).

As another example, the modifier may include a compound represented by the following Chemical Formula 8.

[Formula 8]

In Formula 8, R ⁴³ , R ⁴⁵ and R ⁴⁶ may each independently be an alkyl group ^{having 1 to 10 carbon atoms, R 44} may be an alkylene group having 1 to 10 carbon atoms, and k may be an integer selected from 1 to 4 have.

As a more specific example, the compound represented by Formula 8 is 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13- disila-8-stanpentadecane (8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane); 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8,8- dimetyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane), 8,8-dibutyl-3,3,13, 13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8,8-dibutyl-3,3,13,13-tetramethoxy-2 ,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane) and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl) Propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8-butyl-3,3,13,13-tetramethoxy-8-(( 3-(trimehtoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane) may be selected from the group consisting of).

As another example, the (S2) denaturation reaction may be carried out under the same temperature and pressure conditions as those of the polymerization reaction, and as a specific example, it may be carried out at a temperature of 20° C. to 100° C., and the viscosity of the polymer increases within this range. There is an effect that the activated end of the polymer is not deactivated.

The step (S3) is a step of preparing a polymerization filtrate by separating and removing the low-boiling-point compound from the polymer. The polymer is steam stripped to separate and remove low-boiling-point compounds such as hydrocarbon solvents and unreacted monomers from the polymer. can In this case, the polymerization filtrate may represent a polymer in a crumb state containing moisture.

The steam stripping may be performed under atmospheric conditions of 90°C to 110°C. Here, the atmospheric pressure condition is a pressure without separately reducing or increasing the pressure, and may indicate an atmospheric pressure of about 1 atmosphere (atm). On the other hand, in the present invention, the steam stripping is performed under normal pressure conditions, but in some cases, the inside of the reactor may be in a pressurized state by steam during the steam stripping. It may include up to a pressure increase due to a pressure phenomenon that occurs naturally during stripping.

In addition, the step (S4) is a step for preparing a modified conjugated diene-based polymer by dehydrating and drying the polymerization filtrate, and the dehydration and drying may be performed at a temperature and pressure of 50°C to 180°C. Here, the pressurization condition represents a pressure condition higher than the normal pressure condition, and is not particularly limited and may be pressurized in an appropriate range so that dehydration and drying can be easily performed under the temperature condition.

In addition, the dehydration and drying may be performed using a dehydration apparatus and a drying apparatus conventional in the art, for example, the dehydration may be performed using an expander and an expander, and the drying is It can be carried out using various types of dryers.

Meanwhile, in the manufacturing method according to an embodiment of the present invention, in performing step (S4), the polymerization filtrate contains a sorbitan derivative compound at at least one time point among before dehydration, during dehydration, and before drying after dehydration. It may be to further perform the step of adding the solution.

The dehydration and drying process is generally performed through at least one dehydration step using a dehydrating device and a drying step using a drying device. According to the manufacturing method according to the above step (S4), by adding a solution containing a sorbitan derivative compound to the polymerization filtrate at at least one point of time before dehydration, during dehydration, and before drying after dehydration, the polymerization is performed during the dehydration and drying process. The phenomenon of the filtrate sticking to the dewatering and drying equipment can be reduced, which can significantly reduce the polymer lost.

Specifically, the solution containing the sorbitan derivative compound may be prepared by mixing the sorbitan derivative compound in a polar solvent, wherein the solution containing the sorbitan derivative compound contains the sorbitan derivative compound in an amount of 0.1 wt% to 10 wt% may be doing Here, the polar solvent may be at least one selected from the group consisting of water, methanol, ethanol, acetic acid and acetone, and preferably water.

In addition, the sorbitan derivative compound may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1, 5≤w+x+y+z≤20.

Specifically, the compound represented by Formula 1 is polyethylene glycol sorbitan monolaurate, and w, x, y, and z are independently integers from 1 to 10, w+x+y+ It may have a number suitably selected so that z is an integer of 5 or more and 20 or less.

In addition, the sorbitan derivative compound-containing solution may be added in an amount of 0.001 to 1.000 parts by weight based on 100 parts by weight of the polymerization filtrate, wherein the addition is performed by spraying the sorbitan derivative compound-containing solution to the polymerization filtrate. it could be

In the manufacturing method according to an embodiment of the present invention, the polymer lost in the dehydration and drying process is significantly reduced by performing the method as described above, so that the modified conjugated diene-based polymer can be prepared in a high yield, and specifically, the following formula The relative loss ratio (%) of the modified conjugated diene-based polymer defined as 1 may be 50% or less.

[Equation 1]

Relative loss rate (%)=[100-Polymer A(%)]/[100-Polymer B(%)]×100

In Equation 1 above,

Polymer A is the yield of a modified conjugated diene-based polymer prepared by adding a solution containing a sorbitan derivative compound by the method of the present invention, and Polymer B is a modified conjugated diene-based polymer prepared without adding a solution containing a sorbitan derivative compound. is the yield of

In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer prepared by the above manufacturing method, and a molded article prepared from the rubber composition.

The rubber composition may include the modified conjugated diene-based copolymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and tensile strength, abrasion resistance within this range It is excellent in mechanical properties, such as, and there is an effect excellent in the balance between each physical property.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based copolymer, wherein the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-) propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based copolymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving the breaking properties and wet Wet silica may be the most excellent in compatibility with wet grip. In addition, the rubber composition may further include a carbon-based filler if necessary.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide , bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) propyl) tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, as a rubber component, a modified conjugated diene-based copolymer in which a functional group with high affinity for silica is introduced is used as a rubber component, so the compounding amount of the silane coupling agent is usually may be reduced than in the case of It has the effect of preventing the gelation of the rubber component while sufficiently exhibiting.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. It has an excellent effect.

The rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, an anti-scorch agent, zinc white, It may further include stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. Naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, etc., may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of the tire, such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, chaff, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

In addition, the present invention provides a tire manufactured using the rubber composition.

The tire may include a tire or a tire tread.

Example 1

In the first reactor among the continuous reactors in which three reactors are connected in series, 1.80 kg/hr of a styrene solution in which styrene is dissolved in n-hexane at 60 wt%, and 1,3-butadiene in n-hexane at 60 wt% 14.2 kg/hr of the dissolved 1,3-butadiene solution, 49.11 kg/hr of n-hexane, 40 g/hr of a 1,2-butadiene solution in which 1,2-butadiene was dissolved in 2.0 wt% of n-hexane at 40 g/hr, 51.0 g/hr of a polar additive solution in which 10 wt% of 2,2-di(2-tetrahydrofuryl)propane is dissolved in n-hexane as a polar additive, and 10 wt% of n-butyllithium in n-hexane as a polymerization initiator % of the dissolved initiator solution was continuously added at a rate of 59.0 g/hr. At this time, the internal temperature of the first reactor was maintained at 55° C., and when the polymerization conversion reached 30%, the polymer was transferred from the first reactor to the second reactor.

Then, a 1,3-butadiene solution in which 60 wt% of 1,3-butadiene is dissolved in n-hexane is added to the second reactor at a rate of 0.74 kg/hr, and the internal temperature of the second reactor is 65° C. When the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

Then, the polymer is continuously introduced from the second reactor to the third reactor, and 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis( N,N-dimethylpropane-1-amine)(3,3'-1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine) in 20 wt% The dissolved denaturant solution was continuously introduced into the third reactor at a rate of 100 g/hr to proceed with the denaturation reaction, and the temperature of the third reactor was maintained at 65°C.

Thereafter, a solution of IR1520 (BASF Corporation) dissolved at 30 wt% as an antioxidant was added to the polymerization solution discharged from the third reactor at a rate of 167 g/hr and mixed by passing through a dynamic mixer. The mixed polymerization solution was transferred to a stripper filled with water and then steam stripped under atmospheric pressure at 110°C using steam to remove unreacted monomers and solvents and filtered to obtain a polymerization filtrate in a crumb state containing moisture. . The polymerization filtrate was first and second dehydrated to obtain a dry polymerization filtrate by lowering the moisture content to 3% by weight or less, and a solution containing a sorbitan derivative compound was sprayed thereto in an amount of 0.001 parts by weight relative to 100 parts by weight of the dry polymerization filtrate. After drying, a modified conjugated diene-based polymer was prepared. At this time, the sorbitan derivative compound-containing solution was prepared by dissolving a sorbitan derivative compound (TWEEN ^® 20, CAS No. 9005-64-5, Sigma-Aldrich) at 1 wt % in water.

Example 2

In Example 1, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 0.1 parts by weight of the solution containing the sorbitan derivative compound was sprayed relative to 100 parts by weight of the dry polymerization filtrate.

Example 3

In Example 1, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 0.5 parts by weight of the solution containing the sorbitan derivative compound was sprayed relative to 100 parts by weight of the dry polymerization filtrate.

Example 4

In Example 1, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the sorbitan derivative compound solution was sprayed on the polymerization filtrate in a crumb state, and then dehydrated and dried.

Comparative Example 1

A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that in Example 1, the solution in which the sorbitan derivative compound was dissolved was not sprayed on the polymerization filtrate, and the solution was immediately roll-dried.

Comparative Example 2

In Example 1, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the solution containing the sorbitan derivative compound was put into the stripper during steam stripping.

Experimental Example 1

The yield of the modified conjugated diene-based polymer prepared in Examples and Comparative Examples was analyzed, and the results are shown in Table 1 below.

The yield was compared by analyzing the relative loss rate (%) defined by Equation 2 below.

[Equation 2]

Relative loss rate (%)=[100-Polymer C(%)]/[100-Polymer D(%)]×100

In Equation 2 above,

Polymer C is each yield of the modified conjugated diene-based polymer prepared in Examples 1 to 4 and Comparative Example 2, and Polymer D is the yield of the modified conjugated diene-based polymer prepared in Comparative Example 1.

On the other hand, in the case of the relative loss ratio of the modified conjugated diene-based polymer of Comparative Example 1, both Polymer C and Polymer D were calculated by substituting the yields of the modified conjugated diene-based polymer prepared in Comparative Example 1.

division Example comparative example One 2 3 4 One 2 Relative loss rate (%) 38 21 7 49 100 100

As shown in Table 1, the amount of the modified conjugated diene-based polymer prepared by the manufacturing method of Examples 1 to 4 was significantly reduced by more than half compared to Comparative Examples 1 and 2, and through this, the present invention It was confirmed that the manufacturing method according to the present invention can effectively suppress the loss due to adhesion of the polymer during the dehydration and drying process, and thus the modified conjugated diene-based polymer can be prepared in high yield.

On the other hand, in the case of Comparative Example 2, in which the solution containing the sorbitan derivative compound was added to the stripper during steam stripping, the modified conjugated diene-based polymer was obtained in the same yield as Comparative Example 1 in which the solution containing the sorbitan derivative compound was not added at a relative loss rate of 100%. produced, which means that the loss of the polymer was not inhibited at all during the dehydration and drying process. In addition, it can be seen that the control of the time of addition of the sorbitan derivative compound-containing solution is an important factor in order to suppress the loss of the polymer during dehydration and drying, which is desired in the present invention.

Experimental Example 2

In order to comparatively analyze the physical properties of rubber compositions and molded articles prepared therefrom using the modified conjugated diene-based polymers prepared in Examples and Comparative Examples, tensile properties, viscoelastic properties, and adhesion properties were measured respectively, and the results are shown in the table below. 3 is shown.

1) Preparation of rubber specimens

Each modified or unmodified conjugated diene-based polymer of Examples and Comparative Examples was compounded under the compounding conditions shown in Table 2 below as raw rubber. The content of the raw material in Table 2 is each part by weight based on 100 parts by weight of the raw rubber.

division Raw material Content (parts by weight) 1st stage kneading Rubber 100 silica 70 Coupling agent (X50S) 11.2 fair oil 37.5 Zincizing agent 3 stearic acid 2 antioxidant 2 anti-aging agent 2 wax One 2nd stage kneading sulfur 1.5 rubber accelerator 1.75 vulcanization accelerator 2

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zincating agent (ZnO), stearic acid using a Banbari mixer with temperature control device is used. , antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) ) was kneaded. At this time, the initial temperature of the kneader was controlled to 70° C., and after the mixing was completed, a first formulation was obtained at a discharge temperature of 145° C. to 155° C. In the second stage of kneading, the first formulation was cooled to room temperature. After mixing, the primary compound, sulfur, a rubber accelerator (DPD (diphenylguanine)) and a vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and the temperature of 100° C. or less A secondary formulation was obtained by mixing in. Then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

2) Tensile properties

For tensile properties, each test piece was prepared according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece and the tensile stress (300% modulus) at 300% elongation were measured. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester.

3) Viscoelastic properties

For the viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60°C to 60°C) in Film Tension mode using a dynamic mechanical analyzer (GABO). In the measurement result, the higher the low temperature 0℃ tan value, the better the wet road resistance. Since the result value is expressed as an index based on Comparative Example 1, the higher the numerical value, the better.

4) Adhesive properties

The adhesive properties were confirmed using a Tack Tester (Picma Tack Tester, Toyo Seiki Seisaku-Sho, Japan). Specifically, each rubber specimen was milled 5 times with a roll mill interval of 0.5 mm and a temperature of 50° C. to obtain a wide sheet, and then the sheet was cut into a size of 10.0×200 mm to prepare a specimen. One specimen was placed at the bottom of the tack tester, and one was attached to the main body pick-up ring, and then the adhesive properties were measured. At this time, the adhesive properties were measured 10 times, and the average values excluding the maximum and minimum values were expressed.

division Example comparative example One 2 3 4 One 2 Tensile properties
(Index, %) tensile strength
101 100 100 101 100 101 300% modulus
100 100 101 101 100 100 Viscoelastic properties
(Index, %) tan δ
(at 0°C) 100 100 101 100 100 99 tan δ
(at 60℃) 101 101 101 100 100 100 Adhesive properties (kgf) 0.090 0.087 0.087 0.093 0.087 0.090

In Table 3, the tensile properties of Examples 1 to 4 and Comparative Examples 2 and tan δ at 0° C. were calculated by the following Equation 3 using the measured values of Comparative Example 1 as a reference value, Examples 1 to 4 and Comparative Examples The tan δ at 60° C. of Example 2 was calculated by Equation 4 below using the measured value of Comparative Example 1 as a reference value.

[Equation 3]

Index(%)=(measured value/reference value)×100

[Equation 4]

Index(%)=(reference value/measurement value)×100

As shown in Table 3, each of the modified conjugated diene-based polymers prepared in Examples 1 to 4 had superior tensile properties and viscoelasticity equal to or greater than those of the modified conjugated diene-based polymers prepared in Comparative Examples 1 and 2 properties were exhibited, and at the same time, adhesion properties were also excellent.

Through the results of Tables 1 and 3, the production method according to the present invention includes adding a sorbitan derivative compound-containing solution at at least one point of time before dehydration, during dehydration, and before drying after dehydration, whereby dehydration and drying are performed. It was confirmed that by reducing the polymer lost due to adhesion in the process, it is possible to prepare the modified conjugated diene-based polymer in high yield, as well as maintain excellent physical properties of the modified conjugated diene-based polymer.

Claims (10)

Preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon-based solvent in the presence of a polymerization initiator (S1);
preparing a polymer containing the modified polymer by reacting the active polymer with a modifier (S2);
steam stripping the polymer to prepare a polymerization filtrate from which low boiling point compounds are removed (S3); and
Dehydrating and drying the polymerization filtrate (S4),
A method for producing a modified conjugated diene-based polymer wherein a solution containing a sorbitan derivative compound is added to the polymerization filtrate at at least one point of time before dehydration, during dehydration, and before drying after dehydration in step (S4).
According to claim 1,
The sorbitan derivative compound-containing solution is a method for producing a modified conjugated diene-based polymer prepared by mixing a sorbitan derivative compound in a polar solvent.
3. The method of claim 2,
The polar solvent is a method for producing a modified conjugated diene-based polymer is water.
According to claim 1,
The sorbitan derivative compound-containing solution is a method for producing a modified conjugated diene-based polymer comprising 0.1 wt% to 10 wt% of the sorbitan derivative compound.
According to claim 1,
The method for producing a modified conjugated diene-based polymer wherein the sorbitan derivative compound is a compound represented by the following formula (1):
[Formula 1]

In Formula 1, 5≤w+x+y+z≤20.
According to claim 1,
The method for producing a modified conjugated diene-based polymer, wherein the sorbitan derivative compound-containing solution is added in an amount of 0.001 to 1.000 parts by weight based on 100 parts by weight of the polymerization filtrate.
According to claim 1,
The addition of the sorbitan derivative compound-containing solution is a method for producing a modified conjugated diene-based polymer that is performed by spraying the sorbitan derivative compound-containing solution on the polymerization filtrate.
According to claim 1,
The method for producing a modified conjugated diene-based polymer that the modifying agent is an alkoxysilane-based compound.
According to claim 1,
The polymerization of the step (S1) is a method for producing a modified conjugated diene-based polymer to be carried out by further using a polar additive.
10. The method of claim 9,
The polar additive is tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether, t -Butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethylether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine , Sodium mentholate (sodium mentholate) and 2-ethyl tetrahydrofurfuryl ether (2-ethyl tetrahydrofurfuryl ether) method for producing a modified conjugated diene-based polymer at least one selected from the group consisting of.

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